CN115466968A - An electrolytic hydrogen production system without pure water - Google Patents

Abstract

The invention belongs to the technical field of electrolytic hydrogen production, in particular to an electrolytic hydrogen production system without pure water. The system includes an energy supply module, an electrolytic hydrogen production module and an electrolyte circulation regeneration module, wherein the energy supply module is connected with the electrolysis hydrogen production module, and the electrolyte circulation regeneration module is connected with the electrolysis hydrogen production module. Since in the present invention, all the water supplemented to the electrolyte in the energy-free mass transfer device is impurity-free water, it breaks through the bottleneck of high dependence on pure water for hydrogen production by electrolysis of water, and the direct production of hydrogen from non-pure aqueous solution is not affected by the composition of the solution. Influenced by factors such as time, climate, human activities, etc., at the same time, this system method can be used for electrolytic hydrogen production in non-pure water environments such as sea water, river water, lake water, industrial wastewater, domestic sewage, etc., which greatly broadens the source range of hydrogen energy , and is not restricted by time and space. The invention can realize the internal self-circulation of the electrolyte without supplementing electrolyte and pure water therein.

Description

An electrolytic hydrogen production system without pure water

technical field

The invention belongs to the technical field of electrolytic hydrogen production, in particular to an electrolytic hydrogen production system without pure water.

Background technique

Hydrogen energy has the advantages of wide sources, storability, multiple uses, zero carbon, zero pollution, and high energy density. It is a key component of the future energy field. At present, there are two kinds of electrolysis of water to obtain hydrogen energy. One is to use natural sea water, river water or lake water to directly produce hydrogen by electrolysis, which has the following problems:

(1) The composition is complex, and the composition will change with factors such as season, climate, temperature, region and human activities. Therefore, electrolysis devices for direct hydrogen production from non-pure water in different regions cannot be directly compatible;

(2) The solution is rich in Cl ^- , and in the electrolysis reaction, Cl ^- can be oxidized in the oxygen evolution reaction to produce toxic, environmentally harmful and corrosive ClO ^- and Cl ₂ ;

(3) The concentration of H ⁺ and OH ^- ions is small when the non-pure aqueous solution is directly producing hydrogen, or the buffer molecules cannot transport OH ^- and H ⁺ at the cathode and anode respectively, resulting in low electrolysis efficiency, so additional additives or ion exchange are required Membrane, thus greatly increasing the cost;

(4) Complex components such as impurity ions, microorganisms, and organic matter in impure aqueous solution can easily clog and contaminate ion exchange membranes, and even cause membrane inactivation, thereby greatly increasing maintenance costs in the later stage;

(4) Due to the local pH difference during electrolysis may cause precipitation with calcium and magnesium ions, etc., it is necessary to use acid for precipitation treatment, resulting in additional costs.

The second is to desalinate/purify the impure aqueous solution to produce pure water for hydrogen production by electrolysis. Still taking seawater as an example, seawater desalination is required. This method requires the establishment of seawater desalination plants on the coast, which greatly increases the cost in terms of construction, operation, manpower, and maintenance; Hydrogen production system for stable storage of renewable energy.

Contents of the invention

The purpose of the present invention is to provide an electrolytic hydrogen production system that does not require pure water, aiming at the bottleneck of the prior art. The system can directly obtain pure water from various impure waters such as seawater, river water, lake water, industrial wastewater, and domestic sewage through electrolytes for hydrogen production. This invention can fundamentally solve the problems of ion exchange membrane failure, catalyst deactivation, precipitation and toxic gas due to complex ion composition; save desalination/purification plant equipment investment and desalination/purification cost; at the same time, it will help the future hydrogen energy conversion Not limited by time and space, it provides strong technical support for the direct hydrogen production of impure aqueous solution.

In order to realize above object of the invention, concrete technical scheme of the present invention is:

An electrolytic hydrogen production system that does not require pure water, the system includes an energy supply module, an electrolytic hydrogen production module and an electrolyte cycle regeneration module, wherein:

The energy supply module is connected with the electrolytic hydrogen production module, and is used to provide electric energy for the hydrogen production reaction;

Electrolytic hydrogen production module, which includes an electrolytic cell, after the electrolyte is passed into the electrolytic cell, a redox reaction occurs, water is consumed, and hydrogen and oxygen are produced;

The electrolyte cycle regeneration module is used to directly use impure aqueous solution to replenish pure water in the electrolyte, and is connected with the electrolytic hydrogen production module.

Further, the energy source of the energy supply module in the system is traditional coal electricity or electricity converted from renewable energy.

Preferably, the electrolyzer is any one of the alkaline (AWE) electrolyzer, the proton exchange membrane (PEM) electrolyzer, the anion exchange membrane (AEM) electrolyzer, or any one of the electrolyzers is connected in series or in parallel formed combination. The electrolyte filled in the electrolyzer is a liquid electrolyte or a solid gel electrolyte; the liquid electrolyte is a liquid with relatively low saturation and the function of absorbing water vapor; the solid electrolyte is a substance that induces phase change and liquefaction of water vapor.

Furthermore, the electrolyte circulation regeneration module in this system is a module that realizes the "liquid-gas-liquid" phase change migration process, and uses impure aqueous solution to directly supplement pure water into a relatively high-concentration electrolyte solution, including a mass transfer device without energy consumption. The energy-free mass transfer device is a device in which a waterproof and breathable layer divides the space into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber. When the electrolyte and impure aqueous solution flow close to the waterproof and breathable layer, the interface between the two is saturated with water vapor The pressure difference causes the phase change and gasification of the impure aqueous solution, and the generated water vapor enters the electrolyte mass transfer chamber through the waterproof and breathable layer, and induces the liquefaction of the water vapor to undergo a secondary phase change under the action of the interface vapor pressure difference, realizing the "liquid-gas -The process of phase change and migration of "liquid"; in addition, the waterproof and breathable layer blocks the impurities in the impure aqueous solution and prevents the mutual penetration and pollution of the electrolyte and the impure aqueous solution.

The impure aqueous solution mass transfer cavity of the electrolyte cycle regeneration module is filled with an impure aqueous solution selected from seawater, river water, lake water, waste water or domestic sewage. The electrolyte filled in the electrolyte mass transfer chamber is the same as the electrolyte filled in the electrolyzer.

Preferably, the waterproof and breathable layer is a commercially mature waterproof and breathable layer, or any one selected from porous TPU film, PDMS, PTFE film, or graphene, PVDF particles, PTFE particles by spraying, screen printing or electrostatic adsorption process The prepared porous waterproof and breathable mass transfer layer.

More preferably, the electrolytic hydrogen production module includes an electrolyzer and an electrolyte thermostat; the electrolyzer and the electrolyte thermostat are in communication.

More preferably, the electrolyte circulation regeneration module includes a mass transfer device without energy consumption, a heat exchanger, a filter, an electrolyte circulation pump, and an electrolyte check valve; the cathode and anode of the electrolytic cell are connected to the heat exchanger, and the heat exchanger is connected to the filter Finally, it is connected with the energy-free mass transfer device; the energy-free mass transfer device is connected with the electrolyte thermostat of the electrolytic hydrogen production module through the electrolyte circulation pump and the electrolyte check valve.

As preferably, the system also includes a hydrogen collection module and an oxygen collection module; wherein the hydrogen collection module includes a hydrogen separator, a hydrogen scrubber, a hydrogen cooler and a hydrogen storage tank; the oxygen collection module includes an oxygen separator, an oxygen scrubber, an oxygen cooling The hydrogen separator and the oxygen storage tank; the hydrogen separator and the oxygen separator are respectively connected with the electrolytic cell, and the hydrogen scrubber, the hydrogen cooler and the hydrogen storage tank are connected in sequence after the hydrogen separator; the oxygen scrubber is connected in sequence after the oxygen separator coolers, oxygen coolers and oxygen storage tanks. It is used to separate the electrolyte/moisture entrained in hydrogen and oxygen, and at the same time to wash, dry and store the collected gas.

More preferably, a hydrogen regulating valve and a check valve are set between the hydrogen scrubber and the hydrogen cooler; an oxygen regulating valve and a check valve are set between the oxygen scrubber and the oxygen cooler.

Preferably, the system also includes a cooling module, which includes a radiator, a cooling water tank and a cooling water pump; the cooling water tank is connected to the radiator, and is connected to the hydrogen separator, the hydrogen scrubber, the hydrogen cooler, and the oxygen separator through the cooling water pump , Oxygen scrubber, oxygen cooler and heat exchanger are connected to provide cooling water and cool some devices of the system.

Further, the electrolyte pumped out of the electrolyzer, as well as the electrolyte collected in the hydrogen separator, oxygen separator, hydrogen scrubber and oxygen scrubber, enter the energy-free mass transfer device after passing through the temperature controller and filter.

In this application, the energy-free mass transfer device is the most important part of the whole system, and it is also a key component that is different from the traditional electrolysis hydrogen production system process. In the energy-free mass transfer device, the space is divided into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber by a waterproof and breathable layer. When the electrolyte and impure aqueous solution flow close to the waterproof and breathable layer, the interface vapor pressure difference between the two makes the The pure aqueous solution undergoes phase change and gasification, and the generated water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the water vapor to liquefy and undergo a secondary phase change under the action of the interface vapor pressure difference, which is a "liquid-gas-liquid" phase change The migration process is a continuous process of directly using impure aqueous solution to supplement pure water into a relatively high-concentration electrolyte; in addition, the waterproof and breathable layer effectively blocks impurities in the impure aqueous solution and prevents mutual penetration and pollution of the electrolyte and the impure aqueous solution . This process continuously replenishes pure water for the electrolyte to be used for electrolysis; electrolysis consumes water at the same time to maintain the interface vapor pressure difference between the electrolyte and the impure aqueous solution in the energy-free mass transfer device, thereby inducing continuous replenishment of water into the electrolyte. The energy-free mass transfer device in the module can be a device with a similar structure to the commercially mature flat-panel membrane distillation reaction mass transfer device, hollow fiber membrane distillation reaction mass transfer device, falling film absorption tower, or a device separated by a waterproof and breathable layer. A mass transfer device with a two-phase or multi-phase independent mass transfer space; or any self-made device with a two-phase or multi-phase independent mass transfer space separated by a waterproof and breathable layer, only the filling material is replaced by impure aqueous solution and electrolyte. Can.

As a preference, the waterproof and breathable layer in the self-made non-energy mass transfer device is preferably any one of porous TPU film, PDMS, PTFE film, or graphene, PVDF particles, PTFE particles are prepared by spraying, screen printing or electrostatic adsorption process The porous waterproof breathable mass transfer layer.

As a preference, the electrolyte filled in the electrolytic cell and the electrolyte mass transfer chamber of the energy-free mass transmitter is a liquid electrolyte or a solid gel electrolyte; wherein the liquid electrolyte is a liquid with a lower saturated water vapor pressure or a function of absorbing water vapor, including alkaline Liquid electrolyte, acidic liquid electrolyte and ionic liquid; alkaline liquid electrolyte selected from KOH solution, K ₂ CO ₃ solution, KHCO ₃ solution, NaOH solution, Na ₂ CO ₃ solution, NaHCO ₃ solution, K ₃ PO ₄ solution, CH ₃ COOK solution, one of alkaline substances such as Ca(OH) ₂ , or their combination. Acidic liquid electrolyte such as one of acidic substances such as H ₂ SO ₄ solution, H ₃ PO ₄ solution, or a combination thereof. Ionic liquids such as: 1-ethyl-3 methylimidazole acetate, etc. Organic hygroscopic liquid: PEG, etc. Among them, the solid electrolyte is a substance that can induce phase change and liquefaction of water vapor. Solid gel electrolytes such as: polyacrylamide hydrogel, polysulfonic acid acrylamide hydrogel, polymethacrylamide hydrogel, polybenzyl acrylic Amide hydrogel, polyphenylacrylamide hydrogel, polyethylacrylamide hydrogel, polytert-butylacrylamide hydrogel, etc., all have hydroxyl, sulfonic acid, carboxyl, amine, ether, etc. One of the hygroscopic gels with hydrophilic groups, or their combination.

The impure aqueous solution temperature controller is arranged between the impure aqueous solution circulation pump and the mass transfer device without energy consumption, and the vapor pressure of the impure aqueous solution can be adjusted by controlling the temperature of the impure aqueous solution.

Preferably, each component in the system device is connected with the control system for automatic control system flow.

Preferably, the energy source of the energy supply module can be traditional coal power, or electric energy converted from renewable energy such as solar energy and wind energy.

An electrolytic hydrogen production system without pure water, characterized in that the system includes an energy supply module, an electrolyzer, a hydrogen separator, a hydrogen scrubber, a hydrogen regulating valve, a hydrogen check valve, a hydrogen cooler, a hydrogen storage tank, an oxygen Separator, oxygen scrubber, oxygen regulating valve, oxygen check valve, oxygen cooler, oxygen storage tank, radiator, cooling water tank, cooling water pump, heat exchanger, filter, energy-free mass transfer device, electrolyte circulation pump, Electrolyte check valve, electrolyte temperature controller, non-pure aqueous solution check valve and impure aqueous solution circulating pump; among them, the energy-free mass transfer device is divided into electrolyte mass transfer chamber and impure aqueous solution mass transfer chamber by a waterproof and breathable layer ; The energy supply module is connected to the cathode and anode of the electrolyzer to provide electric energy; a hydrogen separator is installed on the cathode side of the electrolyzer, and a hydrogen scrubber, a hydrogen regulating valve, a hydrogen check valve, a hydrogen cooler and Hydrogen storage tank; an oxygen separator is installed on the anode side of the electrolyzer, and an oxygen scrubber, an oxygen regulating valve, an oxygen check valve, an oxygen cooler and an oxygen storage tank are arranged in sequence after the oxygen separator; the electrolyzer, the hydrogen separator and The oxygen separator is connected to the heat exchanger, and the heat exchanger is connected to the filter and then connected to the energy-free mass transfer device; the energy-free mass transfer device is connected to the electrolyte thermostat through the electrolyte circulation pump and electrolyte check valve, and the electrolyte temperature The controller is connected to the electrolyzer; the non-pure aqueous solution device enters the energy-free mass transfer device through the non-pure aqueous solution circulation pump and the non-pure aqueous solution check valve; the cooling water tank is connected to the hydrogen separator, hydrogen scrubber, hydrogen cooler, Oxygen separator, oxygen scrubber, oxygen cooler and heat exchanger connections.

Using the electrolytic hydrogen production system without pure water as mentioned above to carry out the electrolytic hydrogen production process without pure water includes the following steps:

First, the electrolyte is passed into the cathode or anode of the electrolytic cell, or the cathode and anode are simultaneously passed into the solution, and a redox reaction occurs to generate hydrogen and oxygen;

If the electrolytic cell is an alkaline electrolytic cell or an AEM electrolytic cell, the electrolyte first undergoes a reduction hydrogen evolution reaction at the cathode, and the generated ^OH- enters the anode through the diaphragm or anion exchange membrane, and undergoes an oxidation reaction to generate oxygen; if the electrolytic cell is a PEM electrolytic cell , then the electrolyte first undergoes an oxidation and oxygen evolution reaction at the anode, producing H ⁺ that enters the cathode through the proton exchange membrane, and undergoes a reduction reaction to generate hydrogen;

The generated hydrogen and oxygen enter the hydrogen separator and the oxygen separator respectively. This process separates the generated hydrogen and oxygen from the electrolyte or moisture; the separated hydrogen and oxygen enter the hydrogen scrubber and the oxygen scrubber respectively. The process further fully cleans the unseparated electrolyte and water in the gas; the cleaned hydrogen enters the hydrogen cooler to dry and cool the hydrogen under the control and regulation of the hydrogen regulating valve and check valve, and then stores it in the hydrogen storage tank ;The cleaned oxygen enters the oxygen cooler to dry and cool the oxygen under the control and regulation of the oxygen regulating valve and the check valve, and then stores it in the hydrogen storage tank;

The reacted electrolyte in the electrolyzer, as well as the electrolyte separated and recovered from the hydrogen separator, hydrogen scrubber, oxygen separator and oxygen scrubber, all pass through the heat exchanger and remove possible impurities in the filter; except The impurity electrolyte enters the electrolyte chamber in the energy-free mass transfer device, and the impure aqueous solution chamber is continuously fed into the impure aqueous solution chamber. The two chambers are separated by a waterproof and breathable layer, which only allows water vapor to pass through. Liquid water is not allowed to penetrate and pollute each other; at this time, when the electrolyte and the impure aqueous solution pass through the energy-free mass transfer device at the same time, under the action of the vapor pressure difference between the two interfaces, the impure aqueous solution is vaporized on the surface of the waterproof and breathable layer to produce water Steam and water vapor enter the electrolyte side through the waterproof and breathable layer, and under the action of the interface vapor pressure difference, induce the phase change of the water vapor to liquefy into the electrolyte to replenish water; the electrolyte replenished with water recirculates into the electrolytic cell for electrolysis.

The vapor pressure difference between the electrolyte and the impure aqueous solution at the interface between the two is calculated by seawater 0.5M NaCl, and its vapor pressure at room temperature is 3.131kpa; the KOH solution vaporizes at a concentration of 10wt%, 20wt%, 30wt%, 40wt% and 50wt%. The pressure is 2.92kpa, 2.47kpa, 1.89kpa, 1.32kpa and 0.86kpa respectively, and the vapor pressure difference between the two reaches 0.2kpa, 0.66kpa, 1.25kpa, 1.81kpa and 2.27kpa, which can be realized at the interface of the two Under the action of the vapor pressure difference, the impure aqueous solution vaporizes on the surface of the waterproof and breathable layer to generate water vapor, and the water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the phase change of the water vapor to liquefy into the electrolyte to replenish water under the action of the interface vapor pressure difference. In fact, as long as the vapor pressure difference is greater than 0, water molecules will enter the electrolyte from the impure aqueous solution in the form of "liquid-gas-liquid" phase transition migration.

Any of the electrolytic hydrogen production systems without pure water mentioned above is used for the electrolytic hydrogen production of non-pure aqueous solution. At the same time, the energy consumption of electrolysis is equivalent to the energy consumption of hydrogen production by industrial electrolysis of pure water, and there is no need for additional energy consumption of desalination/purification of impure aqueous solution.

Compared with the prior art, the positive effect of the present invention is reflected in:

(1) This system can realize the direct electrolysis hydrogen production process of non-pure aqueous solution, and the energy consumption of electrolysis is equivalent to the energy consumption of industrial electrolysis of pure water, without additional desalination/purification energy consumption.

(2) In the electrolyte cycle regeneration module, the waterproof and breathable layer isolates the electrolyte from the impure aqueous solution to prevent the two from permeating and polluting each other; in addition, the interface vapor pressure difference between the electrolyte and the impure aqueous solution induces the gasification phase transition of the impure aqueous solution , the generated water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the phase change and liquefaction of the water vapor under the action of the interface vapor pressure difference, replenishing the water in the electrolyte for electrolysis; at the same time, the electrolysis consumes water synchronously to maintain the electrolyte and impure The interfacial vapor pressure difference between the aqueous solutions continues to induce moisture from the impure aqueous solution into the electrolyte. The realization of this process enables the system to continuously use impure aqueous solution for hydrogen production.

(3) All devices, devices, and units in the present invention can use existing commercial mature objects, which greatly ensures the stability and feasibility of the system, and because the system is mature, it is easy to quickly realize large-scale preparation.

(4) The present invention can directly use commercial electrolyzers and electrolytes, which greatly improves the conductivity and electrochemical performance of the electrolytic system, and avoids the problem of low conductivity and low anode-to-cathode transmission efficiency in direct hydrogen production from impure aqueous solutions.

(5) The system collects hydrogen and oxygen independently, and can collect high-purity hydrogen and oxygen at the same time.

(6) The present invention breaks through the technical bottleneck of traditional non-pure aqueous solution electrolysis hydrogen production, and does not need to carry out impure aqueous solution desalination/purification process, so there is no need to build large-scale desalination/purification plants, which greatly reduces construction, operation, manpower, and maintenance etc. costs. The system can realize the dynamic and continuous process of hydrogen production using any aqueous solution without time-space difference; in addition, it can realize energy conversion and stable storage of non-stable renewable energy, providing technical means for the construction of future energy systems.

Description of drawings

Fig. 1 is the structural representation of a kind of electrolytic hydrogen production system without pure water according to the present invention;

Fig. 2 is the test diagram of the electrolytic hydrogen production stability of impure aqueous solution in the embodiment 1 of the present invention;

Fig. 3 is the test diagram of the electrolytic hydrogen production stability of impure aqueous solution in the embodiment 2 of the present invention;

Fig. 4 is the test diagram of the electrolytic hydrogen production stability of impure aqueous solution in the embodiment 3 of the present invention;

Fig. 5 is the test chart of the electrolytic hydrogen production stability of impure aqueous solution in the embodiment 4 of the present invention;

Fig. 6 is the test chart of the electrolytic hydrogen production stability of impure aqueous solution in the embodiment 5 of the present invention;

Fig. 7 is the test chart of the electrolytic hydrogen production stability of impure aqueous solution in the embodiment 6 of the present invention;

Fig. 8 is the self-made electrolyzer schematic diagram in the embodiment 1 of the present invention;

Fig. 9 is a schematic diagram of a flat film distillation reactor used as a mass transfer device without energy consumption in Examples 2 and 4 of the present invention;

Fig. 10 is a schematic diagram of a vacuum fiber membrane distillation reactor used as a mass transfer device without energy consumption in Example 2 of the present invention.

The marks in Figure 1 and the names of corresponding parts: 1—energy supply module; 2—electrolyzer; 3—hydrogen separator; 4—hydrogen scrubber; 5—hydrogen regulating valve; 6—check valve I; 7—hydrogen Cooler; 8—hydrogen storage tank; 9—oxygen separator; 10—oxygen scrubber; 11—oxygen regulating valve; 12—check valve II; 13—oxygen cooler; 14—oxygen storage tank; 15—radiator ; 16—cooling water tank; 17—cooling water pump; 18—heat exchanger; 19—filter; 20—energy-free mass transfer device; 21—electrolyte circulation pump; 22—check valve III; 24—check valve IV; 25—impure aqueous solution circulation pump; A—electrolyte chamber; B—impure aqueous solution chamber.

detailed description

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail below in conjunction with specific embodiments, but it should not be understood that the scope of the above subject of the present invention is limited to the following examples. Without departing from the above-mentioned technical idea of the present invention, various replacements and changes made according to common technical knowledge and customary means in this field shall be included in the scope of the present invention.

Example 1:

An electrolytic hydrogen production system that does not require pure water, the system includes an energy supply module, an electrolytic hydrogen production module and an electrolyte cycle regeneration module, wherein:

The energy supply module is connected with the electrolytic hydrogen production module, and is used to provide electric energy for the hydrogen production reaction; the energy supply module in this embodiment is a commercial power supply;

The electrolytic hydrogen production module is connected with the electrolyte circulation regeneration module. The module includes a self-made alkaline electrolyzer (as shown in Figure 7); after the electrolyte is passed into the electrolyzer, a redox reaction occurs, water is consumed, and hydrogen and oxygen are produced;

The electrolyte circulation regeneration module is connected with the electrolytic hydrogen production module. The module includes a non-energy mass transferr; the electrolyte in the electrolyzer is fed into the non-energy mass transferr.

The electrolyte cycle regeneration module is used to directly use impure aqueous solution to replenish pure water in the electrolyte. The electrolyte cycle regeneration module is a module that realizes the "liquid-gas-liquid" phase change migration process, and uses impure aqueous solution directly to a relatively high-concentration electrolyte solution. Replenishes pure moisture.

In the energy-free mass transfer device, the space is divided into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber by a waterproof and breathable layer. When the electrolyte and impure aqueous solution flow close to the waterproof and breathable layer, the interface vapor pressure difference between the two makes the The pure aqueous solution undergoes a phase change gasification, and the generated water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the water vapor liquefaction to undergo a secondary phase change under the action of the interface vapor pressure difference, which is a "liquid-gas-liquid" phase change The migration process is a continuous process of directly using impure aqueous solution to supplement pure water into a relatively high-concentration electrolyte; in addition, the waterproof and breathable layer effectively blocks impurities in the impure aqueous solution and prevents mutual penetration and pollution of the electrolyte and the impure aqueous solution . This process continuously replenishes pure water for the electrolyte to be used for electrolysis; electrolysis consumes water at the same time to maintain the interface vapor pressure difference between the electrolyte and the impure aqueous solution in the energy-free mass transfer device, thereby inducing continuous replenishment of water into the electrolyte. Energy-free mass transfer devices such as commercially mature flat-panel membrane distillation reaction mass transfer devices or hollow fiber membrane distillation reaction mass transfer devices, falling film absorption towers, etc., which have two-phase or multi-phase independent mass transfer spaces separated by waterproof and air-permeable layers, can be used. Mass transfer device; or any self-made device with a two-phase or multi-phase independent mass transfer space separated by a waterproof and breathable layer, only by replacing the filled material with an electrolyte and an impure aqueous solution. The generated electrolyte enters the electrolyzer again for the electrolytic hydrogen production reaction.

Specific operation: PTFE porous waterproof and breathable membrane is used as the waterproof and breathable layer in the energy-free mass transferr, 30wt% potassium hydroxide solution is used as the electrolyte solution, nickel-molybdenum foam is used as the anode catalyst, nickel-platinized mesh is used as the cathode catalyst, polysulfone membrane As a diaphragm, the non-pure aqueous solution (Jiang'an River water) and the electrolyte solution are both at room temperature. Figure 2 is tested under the condition of 250mA/cm ² . The seawater seawater is calculated as 0.5M NaCl, its vapor pressure at room temperature is 3.131kPa, the vapor pressure of KOH solution is 1.89kPa when the concentration is 30wt%, and the vapor pressure difference between the two is 1.25kPa. The device operated stably for 72 hours in the water of Jiang'an River, and the actual voltage of the stack was about 2.08V.

Using other embodiments of the system, the method steps are the same as in Embodiment 1, and the differences are shown in Table 1

Example 2:

As shown in Figure 1, an electrolytic hydrogen production system that does not require pure water, the system includes an energy supply module, an electrolytic hydrogen production module, and an electrolyte cycle regeneration module, in which:

The energy supply module is connected with the electrolytic hydrogen production module, and is used to provide electric energy for the hydrogen production reaction; the energy supply module in this embodiment is a commercial power supply;

The electrolytic hydrogen production module includes a self-made alkaline electrolytic cell (as shown in Figure 7, which is composed of 11 electrolytic units connected in parallel. One electrolytic unit includes a cathode and an anode separated by a diaphragm. The anode is nickel-molybdenum foam, and the cathode is nickel-plated platinum. , the diaphragm is a polysulfone porous membrane); after the electrolyte is passed into the electrolyzer, a redox reaction occurs, water is consumed, and hydrogen and oxygen are produced;

The electrolyte cycle regeneration module is used to directly use impure aqueous solution to replenish pure water in the electrolyte, and is connected with the electrolytic hydrogen production module. The electrolyte cycle regeneration module is a module that realizes the "liquid-gas-liquid" phase change migration process, and uses impure aqueous solution to directly supplement pure water to a relatively high-concentration electrolyte solution, including a mass transfer device without energy consumption.

The system also includes a hydrogen collection module and an oxygen collection module; wherein the hydrogen collection module includes a hydrogen separator, a hydrogen scrubber, a hydrogen cooler and a hydrogen storage tank; the oxygen collection module includes an oxygen separator, an oxygen scrubber, an oxygen cooler and an oxygen storage tank; the hydrogen separator and the oxygen separator are respectively connected to the electrolytic cell, and the hydrogen scrubber, the hydrogen cooler and the hydrogen storage tank are connected in sequence after the hydrogen separator; the oxygen scrubber, the oxygen gas separator are connected in sequence after the oxygen separator cooler and oxygen storage tank. It is used to separate the electrolyte/moisture entrained in hydrogen and oxygen, and at the same time to wash, dry and store the collected gas.

A hydrogen regulating valve and a check valve are set between the hydrogen scrubber and the hydrogen cooler; an oxygen regulating valve and a check valve are set between the oxygen scrubber and the oxygen cooler.

Further, the system also includes a cooling module, which includes a radiator, a cooling water tank, and a cooling water pump; the cooling water tank is connected to the radiator, and is connected to the hydrogen separator, the hydrogen scrubber, the hydrogen cooler, and the oxygen separator through the cooling water pump , Oxygen scrubber, Oxygen cooler and heat exchanger connections for providing cooling water to keep it in a cooling environment.

Further, the electrolyte cycle regeneration module includes a non-energy mass transferr composed of an electrolyte chamber and an impure aqueous solution chamber, an electrolyte circulation pump, an impure aqueous solution circulation pump, a heat exchanger and a filter; A waterproof and breathable layer is set between the electrolyte chamber of the mass transferer and the non-pure aqueous solution chamber; the electrolytic cell is connected to the heat exchanger and then passes through a filter to enter the electrolyte chamber and non-pure aqueous solution chamber of the energy-free mass transferr The impure aqueous solution is communicated with the impure aqueous solution through the check valve and the impure aqueous solution circulation pump, and the electrolyte chamber is connected with the electrolytic hydrogen production module through the electrolyte circulation pump and the check valve.

Further, the electrolyte pumped out of the electrolyzer, as well as the electrolyte collected in the hydrogen separator, oxygen separator, hydrogen scrubber and oxygen scrubber, enter the energy-free mass transfer device after passing through the heat exchanger and filter.

In the energy-free mass transfer device, the space is divided into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber by a waterproof and breathable layer. When the electrolyte and impure aqueous solution flow close to the waterproof and breathable layer, the interface vapor pressure difference between the two makes the The pure aqueous solution undergoes a phase change gasification, and the generated water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the water vapor liquefaction to undergo a secondary phase change under the action of the interface vapor pressure difference, which is a "liquid-gas-liquid" phase change The migration process is a continuous process of directly using impure aqueous solution to supplement pure water into a relatively high-concentration electrolyte; in addition, the waterproof and breathable layer effectively blocks impurities in the impure aqueous solution and prevents mutual penetration and pollution of the electrolyte and the impure aqueous solution . This process continuously replenishes pure water for the electrolyte to be used for electrolysis; electrolysis consumes water at the same time to maintain the interface vapor pressure difference between the electrolyte and the impure aqueous solution in the energy-free mass transfer device, thereby inducing continuous replenishment of water into the electrolyte. The energy-free mass transfer device in the module can be a commercially mature flat-panel membrane distillation reaction mass transfer device, hollow fiber membrane distillation reaction mass transfer device, falling film absorption tower, etc. A mass transfer device in a mass space; or any self-made device with a two-phase or multi-phase independent mass transfer space separated by a waterproof and gas-permeable layer. The generated electrolyte is adjusted to a suitable temperature under the action of the temperature controller, and then enters the electrolytic cell again for the electrolytic hydrogen production reaction.

The electrolyte solution is 30wt% KOH solution, and the impure aqueous solution is Shenzhen Bay seawater. The effective mass transfer area of the energy-free mass transferer is 1m ² .

First, the electrolyte is passed into the cathode of the electrolyzer (or the anode or cathode and anode are simultaneously passed through), and a redox reaction occurs to generate hydrogen and oxygen. If the electrolytic cell is an alkaline electrolytic cell, the electrolyte first undergoes a reduction hydrogen evolution reaction at the cathode, and the generated ^OH- enters the anode through the diaphragm, and undergoes an oxidation reaction to generate oxygen.

The generated hydrogen and oxygen enter the hydrogen separator 3 and the oxygen separator respectively, and this process separates the generated hydrogen and oxygen from the entrained electrolyte or moisture.

The separated hydrogen and oxygen enter the hydrogen scrubber 4 and the oxygen scrubber respectively, and this process further fully cleans the unseparated electrolyte and water in the gas.

Under the control and regulation of the hydrogen regulating valve and check valve I, the cleaned hydrogen enters the hydrogen cooler to dry and cool the hydrogen, and then stores it in the hydrogen storage tank. The cleaned oxygen enters the oxygen cooler to dry and cool the oxygen under the control of the oxygen regulating valve and check valve II, and then stores it in the hydrogen storage tank.

The reacted electrolyte in the electrolyzer, as well as the electrolyte separated and recovered from the hydrogen separator, hydrogen scrubber, oxygen separator and oxygen scrubber, all pass through the heat exchanger and remove possible impurities in the filter. The impurity-removed electrolyte enters the electrolyte chamber A in the energy-free mass transfer device, and the impure aqueous solution chamber B is continuously fed with impure aqueous solution. The two chambers are separated by a waterproof and breathable layer, and only water is allowed. The steam passes through, and the liquid water is not allowed to penetrate and pollute each other. At this time, when the electrolyte and the impure aqueous solution pass through the energy-free mass transferer at the same time, under the action of the vapor pressure difference between the two interfaces, the impure aqueous solution gasifies on the surface of the waterproof and air-permeable layer to generate water vapor, and the water vapor enters through the waterproof and air-permeable layer. On the electrolyte side, under the action of the interface vapor pressure difference, the phase change of water vapor is induced to liquefy to replenish water for the electrolyte.

After replenishing water, the electrolyte enters the electrolyte temperature controller through the electrolyte circulation pump and check valve III, and after being adjusted to the optimum temperature for electrolysis, it circulates into the electrolytic cell again to produce hydrogen by electrolysis.

Specific operation: PTFE porous waterproof and breathable membrane is used as the waterproof and breathable layer in the energy-free mass transferr, 30wt% potassium hydroxide solution is used as the electrolyte solution, nickel-molybdenum foam is used as the anode catalyst, nickel-platinized mesh is used as the cathode catalyst, polysulfone membrane As the diaphragm, the non-pure aqueous solution (Shenzhen Bay seawater) and the electrolyte solution are both at room temperature, and tested under the condition of 250mA/cm ² , the experimental results are shown in Figure 3. The seawater seawater is calculated as 0.5M NaCl, its vapor pressure at room temperature is 3.131kPa, the vapor pressure of KOH solution is 1.89kPa when the concentration is 30wt%, and the vapor pressure difference between the two is 1.25kPa. As shown in Figure 3, the device has been operating stably in Shenzhen Bay seawater for 2500 hours, the actual voltage of the stack is about 2.1V, the energy consumption of electrolysis is about 5kWh/Nm ³ H ₂ , and about 386L/h of H ₂ is produced. It shows that the system can stably produce hydrogen without additional energy consumption, and the energy consumption is similar to electrolysis of pure water.

Utilize other embodiments of this system, method step is the same as embodiment 2, difference sees table 2: (seawater is calculated with 0.5M NaCl, and its vapor pressure is 3.131kpa under room temperature; KOH solution is in concentration 10wt%, 20wt%, 30wt% , 40wt% and 50wt% vapor pressure is 2.92kpa, 2.47kpa, 1.89kpa, 1.32kpa and 0.86kpa respectively, the vapor pressure difference between the two reaches 0.2kpa, 0.66kpa, 1.25kpa, 1.81kpa and 2.27kpa respectively )

Example 3:

As shown in Figure 1, an electrolytic hydrogen production system that does not require pure water, the system includes an energy supply module, an electrolytic hydrogen production module, and an electrolyte cycle regeneration module, in which:

The energy supply module is connected with the electrolytic hydrogen production module, and is used to provide electric energy for the hydrogen production reaction; the energy supply module in this embodiment is a commercial power supply;

The electrolytic hydrogen production module is a mature commercial alkaline electrolyzer; after the electrolyte is passed into the electrolyzer, a redox reaction occurs, water is consumed, and hydrogen and oxygen are produced;

The electrolyte cycle regeneration module is used to directly use impure aqueous solution to replenish pure water in the electrolyte, and is connected with the electrolytic hydrogen production module.

The system also includes a hydrogen collection module and an oxygen collection module; wherein the hydrogen collection module includes a hydrogen separator, a hydrogen scrubber, a hydrogen cooler and a hydrogen storage tank; the oxygen collection module includes an oxygen separator, an oxygen scrubber, an oxygen cooler and an oxygen storage tank; the hydrogen separator and the oxygen separator are respectively connected to the electrolytic cell, and the hydrogen scrubber, the hydrogen cooler and the hydrogen storage tank are connected in sequence after the hydrogen separator; the oxygen scrubber, the oxygen gas separator are connected in sequence after the oxygen separator cooler and oxygen storage tank. It is used to separate the electrolyte/moisture entrained in hydrogen and oxygen, and at the same time to wash, dry and store the collected gas.

A hydrogen regulating valve and a check valve are set between the hydrogen scrubber and the hydrogen cooler; an oxygen regulating valve and a check valve are set between the oxygen scrubber and the oxygen cooler.

Further, the system also includes a cooling module, which includes a radiator, a cooling water tank, and a cooling water pump; the cooling water tank is connected to the radiator, and is connected to the hydrogen separator, the hydrogen scrubber, the hydrogen cooler, and the oxygen separator through the cooling water pump , Oxygen scrubber, Oxygen cooler and heat exchanger connections for providing cooling water to keep it in a cooling environment.

Further, the electrolyte cycle regeneration module includes a non-energy mass transferr composed of an electrolyte chamber and an impure aqueous solution chamber, an electrolyte circulation pump, an impure aqueous solution circulation pump, a heat exchanger and a filter; A waterproof and breathable layer is set between the electrolyte chamber of the mass transferer and the non-pure aqueous solution chamber; the electrolytic cell is connected to the heat exchanger and then passes through a filter to enter the electrolyte chamber and non-pure aqueous solution chamber of the energy-free mass transferr The impure aqueous solution is communicated with the impure aqueous solution through the check valve and the impure aqueous solution circulation pump, and the electrolyte chamber is connected with the electrolytic hydrogen production module through the electrolyte circulation pump and the check valve.

Further, the electrolyte pumped out of the electrolyzer, as well as the electrolyte collected in the hydrogen separator, oxygen separator, hydrogen scrubber and oxygen scrubber, enter the energy-free mass transfer device after passing through the heat exchanger and filter.

In the energy-free mass transfer device, the space is divided into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber by a waterproof and breathable layer. When the electrolyte and impure aqueous solution flow close to the waterproof and breathable layer, the interface vapor pressure difference between the two makes the The pure aqueous solution undergoes phase change and gasification, and the generated water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the water vapor to liquefy and undergo a secondary phase change under the action of the interface vapor pressure difference, which is a "liquid-gas-liquid" phase change The migration process is a continuous process of directly using impure aqueous solution to supplement pure water into a relatively high-concentration electrolyte; in addition, the waterproof and breathable layer effectively blocks impurities in the impure aqueous solution and prevents mutual penetration and pollution of the electrolyte and the impure aqueous solution . This process continuously replenishes pure water for the electrolyte to be used for electrolysis; electrolysis consumes water at the same time to maintain the interface vapor pressure difference between the electrolyte and the impure aqueous solution in the energy-free mass transfer device, thereby inducing continuous replenishment of water into the electrolyte. The energy-free mass transfer device in the module can be a commercially mature flat-panel membrane distillation reaction mass transfer device, hollow fiber membrane distillation reaction mass transfer device, falling film absorption tower, etc. A mass transfer device in a mass space; or any self-made device with a two-phase or multi-phase independent mass transfer space separated by a waterproof and gas-permeable layer. The generated electrolyte is adjusted to a suitable temperature under the action of the temperature controller, and then enters the electrolytic cell again for the electrolytic hydrogen production reaction.

The electrolyte solution is 30wt% KOH solution, and the impure aqueous solution is Shenzhen Bay seawater. The effective mass transfer area of the energy-free mass transferer is 1m ² .

First, the electrolyte is passed into the cathode of the electrolytic cell (or the anode and cathode are simultaneously passed through), and a redox reaction occurs to generate hydrogen and oxygen. If the electrolytic cell is an alkaline electrolytic cell, the electrolyte first undergoes a reduction hydrogen evolution reaction at the cathode, and the generated ^OH- enters the anode through the diaphragm, and undergoes an oxidation reaction to generate oxygen.

The generated hydrogen and oxygen enter the hydrogen separator 3 and the oxygen separator 9 respectively, and this process separates the generated hydrogen and oxygen from the entrained electrolyte or moisture.

The separated hydrogen and oxygen enter the hydrogen scrubber and oxygen scrubber respectively, and this process further fully cleans the unseparated electrolyte and water in the gas.

Under the control and regulation of the hydrogen regulating valve and check valve I, the cleaned hydrogen enters the hydrogen cooler to dry and cool the hydrogen, and then stores it in the hydrogen storage tank. The cleaned oxygen enters the oxygen cooler to dry and cool the oxygen under the control of the oxygen regulating valve and check valve II, and then stores it in the hydrogen storage tank.

The reacted electrolyte in the electrolyzer, and the electrolyte separated and recovered from the hydrogen separator 3, the hydrogen scrubber, the oxygen separator 9 and the oxygen scrubber, all pass through the heat exchanger, and remove possible impurities in the filter. Impurities. The impurity-removed electrolyte enters the electrolyte chamber A in the energy-free mass transfer device, and the impure aqueous solution chamber B is continuously fed with impure aqueous solution. The two chambers are separated by a waterproof and breathable layer, and only water is allowed. The steam passes through, and the liquid water is not allowed to penetrate and pollute each other. At this time, when the electrolyte and the impure aqueous solution pass through the energy-free mass transferer at the same time, under the action of the vapor pressure difference between the two interfaces, the impure aqueous solution gasifies on the surface of the waterproof and air-permeable layer to generate water vapor, and the water vapor enters through the waterproof and air-permeable layer. On the electrolyte side, under the action of the interface vapor pressure difference, the phase change of water vapor is induced to liquefy to replenish water for the electrolyte.

After replenishing water, the electrolyte enters the electrolyte temperature controller through the electrolyte circulation pump and check valve III, and after being adjusted to the optimum temperature for electrolysis, it circulates into the electrolytic cell again to produce hydrogen by electrolysis.

Specific operation: PTFE porous waterproof and breathable membrane is used as the waterproof and breathable layer in the energy-free mass transfer device, 30wt% potassium hydroxide solution is used as the electrolyte solution, a commercial alkaline electrolyzer is used as the electrolytic hydrogen production reactor, impure aqueous solution and electrolyte solution Both are at room temperature, and tested under the condition of 250mA/cm ² , the experimental results are shown in Figure 4. The seawater seawater is calculated as 0.5M NaCl, its vapor pressure at room temperature is 3.131kPa, the vapor pressure of KOH solution is 1.89kPa when the concentration is 30wt%, and the vapor pressure difference between the two is 1.25kPa. As shown in Figure 4, the device has been running stably for 2000 hours in seawater of Shenzhen Bay, and the actual voltage of the stack is about 2V. It shows that the system can stably produce hydrogen without additional energy consumption, and the energy consumption is similar to electrolysis of pure water.

Utilize other embodiments of this system, method step is the same as embodiment 3, difference sees table 3: (seawater is calculated with 0.5M NaCl, and its vapor pressure is 3.131kpa under room temperature; KOH solution is in concentration 10wt%, 20wt%, 30wt% , 40wt% and 50wt% vapor pressure is 2.92kpa, 2.47kpa, 1.89kpa, 1.32kpa and 0.86kpa respectively, the vapor pressure difference between the two reaches 0.2kpa, 0.66kpa, 1.25kpa, 1.81kpa and 2.27kpa)

Utilize other embodiments of this system, method step is the same as embodiment 3, difference sees table 4: (seawater is calculated with 0.5M NaCl, and its vapor pressure is 3.131kpa under room temperature; KOH solution is in concentration 10wt%, 20wt%, 30wt% , 40wt% and 50wt% vapor pressure is 2.92kpa, 2.47kpa, 1.89kpa, 1.32kpa and 0.86kpa respectively, the vapor pressure difference between the two reaches 0.2kpa, 0.66kpa, 1.25kpa, 1.81kpa and 2.27kpa)

Embodiment 4:

As shown in Figure 1, an electrolytic hydrogen production system that does not require pure water, the system includes an energy supply module, an electrolytic hydrogen production module, and an electrolyte cycle regeneration module, in which:

The energy supply module is connected with the electrolytic hydrogen production module, and is used to provide electric energy for the hydrogen production reaction; the energy supply module in this embodiment is a commercial power supply;

The electrolytic hydrogen production module is a commercial and mature PEM electrolyzer; after the electrolyte is passed into the electrolyzer, a redox reaction occurs, water is consumed, and hydrogen and oxygen are produced;

The electrolyte cycle regeneration module is used to directly use impure aqueous solution to replenish pure water in the electrolyte, and is connected with the electrolytic hydrogen production module.

The system also includes a hydrogen collection module and an oxygen collection module; wherein the hydrogen collection module includes a hydrogen separator, a hydrogen scrubber, a hydrogen cooler and a hydrogen storage tank; the oxygen collection module includes an oxygen separator, an oxygen scrubber, an oxygen cooler and an oxygen storage tank; the hydrogen separator and the oxygen separator are respectively connected to the electrolytic cell, and the hydrogen scrubber, the hydrogen cooler and the hydrogen storage tank are connected in sequence after the hydrogen separator; the oxygen scrubber, the oxygen gas separator are connected in sequence after the oxygen separator cooler and oxygen storage tank. It is used to separate the electrolyte/moisture entrained in hydrogen and oxygen, and at the same time to wash, dry and store the collected gas.

A hydrogen regulating valve and a check valve are set between the hydrogen scrubber and the hydrogen cooler; an oxygen regulating valve and a check valve are set between the oxygen scrubber and the oxygen cooler.

Further, the system also includes a cooling module, which includes a radiator, a cooling water tank, and a cooling water pump; the cooling water tank is connected to the radiator, and is connected to the hydrogen separator, the hydrogen scrubber, the hydrogen cooler, and the oxygen separator through the cooling water pump , Oxygen scrubber, Oxygen cooler and heat exchanger connections for providing cooling water to keep it in a cooling environment.

Further, the electrolyte cycle regeneration module includes a non-energy mass transferr composed of an electrolyte chamber and an impure aqueous solution chamber, an electrolyte circulation pump, an impure aqueous solution circulation pump, a heat exchanger and a filter; A waterproof and breathable layer is set between the electrolyte chamber of the mass transferer and the non-pure aqueous solution chamber; the electrolytic cell is connected to the heat exchanger and then passes through a filter to enter the electrolyte chamber and non-pure aqueous solution chamber of the energy-free mass transferr The impure aqueous solution is communicated with the impure aqueous solution through the check valve and the impure aqueous solution circulation pump, and the electrolyte chamber is connected with the electrolytic hydrogen production module through the electrolyte circulation pump and the check valve.

Further, the electrolyte pumped out of the electrolyzer, as well as the electrolyte collected in the hydrogen separator, oxygen separator, hydrogen scrubber and oxygen scrubber, enter the energy-free mass transfer device after passing through the heat exchanger and filter.

In the energy-free mass transfer device, the space is divided into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber by a waterproof and breathable layer. When the electrolyte and impure aqueous solution flow close to the waterproof and breathable layer, the interface vapor pressure difference between the two makes the The pure aqueous solution undergoes phase change and gasification, and the generated water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the water vapor to liquefy and undergo a secondary phase change under the action of the interface vapor pressure difference, which is a "liquid-gas-liquid" phase change The migration process is a continuous process of directly using impure aqueous solution to supplement pure water into a relatively high-concentration electrolyte; in addition, the waterproof and breathable layer effectively blocks impurities in the impure aqueous solution and prevents mutual penetration and pollution of the electrolyte and the impure aqueous solution . This process continuously replenishes pure water for the electrolyte to be used for electrolysis; electrolysis consumes water at the same time to maintain the interface vapor pressure difference between the electrolyte and the impure aqueous solution in the energy-free mass transfer device, thereby inducing continuous replenishment of water into the electrolyte. The energy-free mass transfer device in the module can be a commercially mature flat-panel membrane distillation reaction mass transfer device, hollow fiber membrane distillation reaction mass transfer device, falling film absorption tower, etc. A mass transfer device in a mass space; or any self-made device with a two-phase or multi-phase independent mass transfer space separated by a waterproof and gas-permeable layer. The generated electrolyte is adjusted to a suitable temperature under the action of the temperature controller, and then enters the electrolytic cell again for the electrolytic hydrogen production reaction.

The electrolyte solution is 15wt% H ₂ SO ₄ solution, and the impure aqueous solution is Shenzhen Bay seawater. The effective mass transfer area of the energy-free mass transferer is 1m ² .

First, the electrolyte is passed into the anode of the electrolytic cell (or the cathode or cathode and anode are simultaneously passed through), and a redox reaction occurs to generate hydrogen and oxygen. The electrolytic cell is a commercial PEM electrolytic cell, and the electrolyte first undergoes oxidation and oxygen evolution reaction at the anode, and the generated H ⁺ enters the cathode through the cation exchange membrane, and undergoes a reduction reaction to generate hydrogen.

The generated hydrogen and oxygen enter the hydrogen separator and oxygen separator respectively, and this process separates the generated hydrogen and oxygen from the entrained electrolyte or moisture.

The separated hydrogen and oxygen enter the hydrogen scrubber 4 and the oxygen scrubber respectively, and this process further fully cleans the unseparated electrolyte and water in the gas.

Under the control and regulation of the hydrogen regulating valve and check valve I, the cleaned hydrogen enters the hydrogen cooler to dry and cool the hydrogen, and then stores it in the hydrogen storage tank. The cleaned oxygen enters the oxygen cooler to dry and cool the oxygen under the control of the oxygen regulating valve and check valve II, and then stores it in the hydrogen storage tank.

The reacted electrolyte in the electrolyzer, as well as the electrolyte separated and recovered from the hydrogen separator, hydrogen scrubber, oxygen separator and oxygen scrubber, all pass through the heat exchanger and remove possible impurities in the filter . The impurity-removed electrolyte enters the electrolyte chamber A in the energy-free mass transfer device, and the impure aqueous solution chamber B is continuously fed with impure aqueous solution. The two chambers are separated by a waterproof and breathable layer, and only water is allowed. The steam passes through, and the liquid water is not allowed to penetrate and pollute each other. At this time, when the electrolyte and the impure aqueous solution pass through the energy-free mass transferer at the same time, under the action of the vapor pressure difference between the two interfaces, the impure aqueous solution gasifies on the surface of the waterproof and air-permeable layer to generate water vapor, and the water vapor enters through the waterproof and air-permeable layer. On the electrolyte side, under the action of the interface vapor pressure difference, the phase change of water vapor is induced to liquefy to replenish water for the electrolyte.

After replenishing water, the electrolyte enters the electrolyte temperature controller through the electrolyte circulation pump and check valve III, and after being adjusted to the optimum temperature for electrolysis, it circulates into the electrolytic cell again to produce hydrogen by electrolysis.

Specific operation: PTFE porous waterproof and breathable membrane is used as the waterproof and breathable layer in the energy-free mass transfer device, 15wt% sulfuric acid solution is used as the electrolyte solution, and the commercial PEM electrolyzer is used as the electrolytic hydrogen production reactor. Both the impure aqueous solution and the electrolyte solution are at room temperature Temperature, tested under the condition of 250mA/cm ² , the experimental results are shown in Figure 5. As shown in Figure 5, the device has been running stably for 500 hours in seawater of Shenzhen Bay, and the actual voltage of the electrolyzer is about 1.9V. It shows that the system can stably produce hydrogen without additional energy consumption, and the energy consumption is similar to electrolysis of pure water.

Using other embodiments of the system, the method steps are the same as in Embodiment 4, and the differences are shown in Table 5:

Example 5:

As shown in Figure 1, an electrolytic hydrogen production system that does not require pure water, the system includes an energy supply module, an electrolytic hydrogen production module, and an electrolyte cycle regeneration module, in which:

The energy supply module is connected with the electrolytic hydrogen production module, and is used to provide electric energy for the hydrogen production reaction; the energy supply module in this embodiment is a commercial power supply;

The electrolytic hydrogen production module is a mature commercial alkaline electrolyzer; after the electrolyte is passed into the electrolyzer, a redox reaction occurs, water is consumed, and hydrogen and oxygen are produced;

The electrolyte cycle regeneration module is used to directly use impure aqueous solution to replenish pure water in the electrolyte, and is connected with the electrolytic hydrogen production module.

The system also includes a hydrogen collection module and an oxygen collection module; wherein the hydrogen collection module includes a hydrogen separator, a hydrogen scrubber, a hydrogen cooler and a hydrogen storage tank; the oxygen collection module includes an oxygen separator, an oxygen scrubber, an oxygen cooler and an oxygen storage tank; the hydrogen separator and the oxygen separator are respectively connected to the electrolytic cell, and the hydrogen scrubber, the hydrogen cooler and the hydrogen storage tank are connected in sequence after the hydrogen separator; the oxygen scrubber, the oxygen gas separator are connected in sequence after the oxygen separator cooler and oxygen storage tank. It is used to separate the electrolyte/moisture entrained in hydrogen and oxygen, and at the same time to wash, dry and store the collected gas.

A hydrogen regulating valve and a check valve are set between the hydrogen scrubber and the hydrogen cooler; an oxygen regulating valve and a check valve are set between the oxygen scrubber and the oxygen cooler.

Further, the system also includes a cooling module, which includes a radiator, a cooling water tank, and a cooling water pump; the cooling water tank is connected to the radiator, and is connected to the hydrogen separator, the hydrogen scrubber, the hydrogen cooler, and the oxygen separator through the cooling water pump , Oxygen scrubber, Oxygen cooler and heat exchanger connections for providing cooling water to keep it in a cooling environment.

Further, the electrolyte cycle regeneration module includes a non-energy mass transferr composed of an electrolyte chamber and an impure aqueous solution chamber, an electrolyte circulation pump, an impure aqueous solution circulation pump, a heat exchanger and a filter; A waterproof and breathable layer is set between the electrolyte chamber of the mass transferer and the non-pure aqueous solution chamber; the electrolytic cell is connected to the heat exchanger and then passes through a filter to enter the electrolyte chamber and non-pure aqueous solution chamber of the energy-free mass transferr The impure aqueous solution is communicated with the impure aqueous solution through the check valve and the impure aqueous solution circulation pump, and the electrolyte chamber is connected with the electrolytic hydrogen production module through the electrolyte circulation pump and the check valve.

Further, the electrolyte pumped out of the electrolyzer, as well as the electrolyte collected in the hydrogen separator, oxygen separator, hydrogen scrubber and oxygen scrubber, enter the energy-free mass transfer device after passing through the heat exchanger and filter.

In the energy-free mass transfer device, the space is divided into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber by a waterproof and breathable layer. When the electrolyte and impure aqueous solution flow close to the waterproof and breathable layer, the water vapor pressure difference between the two makes the The pure aqueous solution undergoes phase change and gasification, and the generated water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the water vapor to liquefy and undergo a secondary phase change under the action of the interface vapor pressure difference, which is a "liquid-gas-liquid" phase change The migration process is a continuous process in which pure water is directly added to a relatively high-concentration electrolyte solution using an impure aqueous solution; in addition, the waterproof and breathable layer effectively blocks impurities in the impure aqueous solution and prevents the interaction between the electrolyte and the impure aqueous solution. Penetration pollution. This process continuously replenishes pure water for the electrolyte to be used for electrolysis; electrolysis consumes water at the same time to maintain the interface vapor pressure difference between the electrolyte and the impure aqueous solution in the energy-free mass transfer device, thereby inducing continuous replenishment of water into the electrolyte. The energy-free mass transfer device in the module can be a commercially mature flat-panel membrane distillation reaction mass transfer device, hollow fiber membrane distillation reaction mass transfer device, falling film absorption tower, etc. A mass transfer device in a mass space; or any self-made device with a two-phase or multi-phase independent mass transfer space separated by a waterproof and gas-permeable layer. The generated electrolyte is adjusted to a suitable temperature under the action of the temperature controller, and then enters the electrolytic cell again for the electrolytic hydrogen production reaction.

The electrolyte solution is 30wt% KOH solution, and the impure aqueous solution is Shenzhen Bay seawater. The energy-free mass transfer device is a commercial flat-plate membrane distillation reactor (Figure 9, the structure is the same, but the filling materials are impure aqueous solution and electrolyte).

First, the electrolyte is passed into the cathode of the electrolytic cell (or the anode and cathode are simultaneously passed through), and a redox reaction occurs to generate hydrogen and oxygen. If the electrolytic cell is an alkaline electrolytic cell, the electrolyte first undergoes a reduction hydrogen evolution reaction at the cathode, and the generated ^OH- enters the anode through the diaphragm, and undergoes an oxidation reaction to generate oxygen.

The generated hydrogen and oxygen enter the hydrogen separator and oxygen separator respectively, and this process separates the generated hydrogen and oxygen from the entrained electrolyte or moisture.

The separated hydrogen and oxygen enter the hydrogen scrubber and oxygen scrubber respectively, and this process further fully cleans the unseparated electrolyte and water in the gas.

Under the control and regulation of the hydrogen regulating valve and check valve I, the cleaned hydrogen enters the hydrogen cooler to dry and cool the hydrogen, and then stores it in the hydrogen storage tank. The cleaned oxygen enters the oxygen cooler to dry and cool the oxygen under the control of the oxygen regulating valve and check valve II, and then stores it in the hydrogen storage tank.

The reacted electrolyte in the electrolyzer, as well as the electrolyte separated and recovered from the hydrogen separator, hydrogen scrubber, oxygen separator and oxygen scrubber, all pass through the heat exchanger and remove possible impurities in the filter. The impurity-removed electrolyte enters the electrolyte chamber A in the energy-free mass transfer device, and the impure aqueous solution chamber B is continuously fed with impure aqueous solution. The two chambers are separated by a waterproof and breathable layer, and only water is allowed. The steam passes through, and the liquid water is not allowed to penetrate and pollute each other. At this time, when the electrolyte and the impure aqueous solution pass through the energy-free mass transferer at the same time, under the action of the vapor pressure difference between the two interfaces, the impure aqueous solution gasifies on the surface of the waterproof and air-permeable layer to generate water vapor, and the water vapor enters through the waterproof and air-permeable layer. On the electrolyte side, under the action of the interface vapor pressure difference, the phase change of water vapor is induced to liquefy to replenish water for the electrolyte.

After replenishing water, the electrolyte enters the electrolyte temperature controller through the electrolyte circulation pump and check valve III, and after being adjusted to the optimum temperature for electrolysis, it circulates into the electrolytic cell again to produce hydrogen by electrolysis.

Specific operation: 30wt% potassium hydroxide solution is used as the electrolyte solution, the commercial alkaline electrolyzer is used as the electrolytic hydrogen production reactor, and the commercial flat membrane distillation reactor is used as the energy-free mass transfer device. Both the impure aqueous solution and the electrolyte solution are at room temperature, and tested under the condition of 250mA/cm ² , the experimental results are shown in Figure 6. The seawater is calculated as 0.5M NaCl, its vapor pressure at room temperature is 3.131kPa, the vapor pressure of KOH solution is 1.89kPa when the concentration is 30wt%, and the vapor pressure difference between the two is 1.25kPa. As shown in Figure 6, the device has been running stably for 500 hours in seawater of Shenzhen Bay, and the actual voltage of the stack is about 2V. It shows that the system can stably produce hydrogen without additional energy consumption, and the energy consumption is similar to electrolysis of pure water.

Utilize other embodiments of this system, method step is the same as embodiment 5, difference is shown in table 6: (seawater is calculated with 0.5M NaCl, and its room temperature vapor pressure is 3.131kpa; KOH solution is in concentration 10wt%, 20wt%, 30wt% , 40wt% and 50wt% vapor pressure is 2.92kpa, 2.47kpa, 1.89kpa, 1.32kpa and 0.86kpa respectively, the vapor pressure difference between the two reaches 0.2kpa, 0.66kpa, 1.25kpa, 1.81kpa and 2.27kpa)

Embodiment 6:

As shown in Figure 1, an electrolytic hydrogen production system that does not require pure water, the system includes an energy supply module, an electrolytic hydrogen production module, and an electrolyte cycle regeneration module, in which:

The energy supply module is connected with the electrolytic hydrogen production module, and is used to provide electric energy for the hydrogen production reaction; the energy supply module in this embodiment is a commercial power supply;

The electrolytic hydrogen production module is an alkaline electrolyzer; after the electrolyte is passed into the electrolyzer, a redox reaction occurs, water is consumed, and hydrogen and oxygen are produced;

The electrolyte cycle regeneration module is used to directly use impure aqueous solution to replenish pure water in the electrolyte, and is connected with the electrolytic hydrogen production module.

The system also includes a hydrogen collection module and an oxygen collection module; wherein the hydrogen collection module includes a hydrogen separator, a hydrogen scrubber, a hydrogen cooler and a hydrogen storage tank; the oxygen collection module includes an oxygen separator, an oxygen scrubber, an oxygen cooler and an oxygen storage tank; the hydrogen separator and the oxygen separator are respectively connected to the electrolytic cell, and the hydrogen scrubber, the hydrogen cooler and the hydrogen storage tank are connected in sequence after the hydrogen separator; the oxygen scrubber, the oxygen gas separator are connected in sequence after the oxygen separator cooler and oxygen storage tank. It is used to separate the electrolyte/moisture entrained in hydrogen and oxygen, and at the same time to wash, dry and store the collected gas.

A hydrogen regulating valve and a check valve are set between the hydrogen scrubber and the hydrogen cooler; an oxygen regulating valve and a check valve are set between the oxygen scrubber and the oxygen cooler.

Further, the system also includes a cooling module, which includes a radiator, a cooling water tank, and a cooling water pump; the cooling water tank is connected to the radiator, and is connected to the hydrogen separator, the hydrogen scrubber, the hydrogen cooler, and the oxygen separator through the cooling water pump , Oxygen scrubber, Oxygen cooler and heat exchanger connections for providing cooling water to keep it in a cooling environment.

Further, the electrolyte cycle regeneration module includes a non-energy mass transferr composed of an electrolyte chamber and an impure aqueous solution chamber, an electrolyte circulation pump, an impure aqueous solution circulation pump, a heat exchanger and a filter; A waterproof and breathable layer is set between the electrolyte chamber of the mass transferer and the non-pure aqueous solution chamber; the electrolytic cell is connected to the heat exchanger and then passes through a filter to enter the electrolyte chamber and non-pure aqueous solution chamber of the energy-free mass transferr The impure aqueous solution is communicated with the impure aqueous solution through the check valve and the impure aqueous solution circulation pump, and the electrolyte chamber is connected with the electrolytic hydrogen production module through the electrolyte circulation pump and the check valve.

Further, the electrolyte pumped out of the electrolyzer, as well as the electrolyte collected in the hydrogen separator, oxygen separator, hydrogen scrubber and oxygen scrubber, enter the energy-free mass transfer device after passing through the heat exchanger and filter.

In the energy-free mass transfer device, the space is divided into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber by a waterproof and breathable layer. When the electrolyte and impure aqueous solution flow close to the waterproof and breathable layer, the water vapor pressure difference between the two makes the The pure aqueous solution undergoes phase change and gasification, and the generated water vapor enters the electrolyte side through the waterproof and breathable layer, and induces the water vapor to liquefy and undergo a secondary phase change under the action of the interface vapor pressure difference, which is a "liquid-gas-liquid" phase change The migration process is a continuous process in which pure water is directly added to a relatively high-concentration electrolyte solution using an impure aqueous solution; in addition, the waterproof and breathable layer effectively blocks impurities in the impure aqueous solution and prevents the interaction between the electrolyte and the impure aqueous solution. Penetration pollution. This process continuously replenishes pure water for the electrolyte to be used for electrolysis; electrolysis consumes water at the same time to maintain the interface vapor pressure difference between the electrolyte and the impure aqueous solution in the energy-free mass transfer device, thereby inducing continuous replenishment of water into the electrolyte. The energy-free mass transfer device in the module can be a commercially mature flat-panel membrane distillation reaction mass transfer device, hollow fiber membrane distillation reaction mass transfer device, falling film absorption tower, etc. A mass transfer device in a mass space; or any self-made device with a two-phase or multi-phase independent mass transfer space separated by a waterproof and gas-permeable layer. The generated electrolyte is adjusted to a suitable temperature under the action of the temperature controller, and then enters the electrolytic cell again for the electrolytic hydrogen production reaction.

The electrolyte solution is 50wt% KOH solution, and the impure aqueous solution is Shenzhen Bay seawater. The energy-free mass transfer device is a commercial flat-plate membrane distillation reactor (Figure 9, the structure is the same, but the filling materials are impure aqueous solution and electrolyte).

First, the electrolyte is passed into the cathode of the electrolytic cell (or the anode and cathode are simultaneously passed through), and a redox reaction occurs to generate hydrogen and oxygen. If the electrolytic cell is an alkaline electrolytic cell, the electrolyte first undergoes a reduction hydrogen evolution reaction at the cathode, and the generated ^OH- enters the anode through the diaphragm, and undergoes an oxidation reaction to generate oxygen.

The generated hydrogen and oxygen enter the hydrogen separator and oxygen separator respectively, and this process separates the generated hydrogen and oxygen from the entrained electrolyte or moisture.

The separated hydrogen and oxygen enter the hydrogen scrubber and oxygen scrubber respectively, and this process further fully cleans the unseparated electrolyte and water in the gas.

Under the control and regulation of the hydrogen regulating valve and check valve I, the cleaned hydrogen enters the hydrogen cooler to dry and cool the hydrogen, and then stores it in the hydrogen storage tank. The cleaned oxygen enters the oxygen cooler to dry and cool the oxygen under the control of the oxygen regulating valve and check valve II, and then stores it in the hydrogen storage tank.

The reacted electrolyte in the electrolyzer, as well as the electrolyte separated and recovered from the hydrogen separator, hydrogen scrubber, oxygen separator and oxygen scrubber, all pass through the heat exchanger and remove possible impurities in the filter. The impurity-removed electrolyte enters the electrolyte chamber A in the energy-free mass transfer device, and at the same time, the impure aqueous solution chamber B is continuously fed with the impure aqueous solution regulated by the thermostat, and the two chambers are separated by a waterproof The air-permeable layer is separated, only water vapor is allowed to pass through, and liquid water is not allowed to penetrate and pollute each other. At this time, when the electrolyte and the impure aqueous solution pass through the energy-free mass transferer at the same time, under the action of the vapor pressure difference between the two interfaces, the impure aqueous solution gasifies on the surface of the waterproof and air-permeable layer to generate water vapor, and the water vapor enters through the waterproof and air-permeable layer. On the electrolyte side, under the action of the interface vapor pressure difference, the phase change of water vapor is induced to liquefy to replenish water for the electrolyte.

After replenishing water, the electrolyte enters the electrolyte temperature controller through the electrolyte circulation pump and check valve III, and after being adjusted to the optimum temperature for electrolysis, it circulates into the electrolytic cell again to produce hydrogen by electrolysis.

Specific operation: 50wt% potassium hydroxide solution is used as the electrolyte solution, the alkaline electrolyzer is used as the electrolytic hydrogen production reactor, and the commercial flat membrane distillation reactor (consistent in structure, but the filling material is impure aqueous solution and electrolyte) is used as the energy-free mass transfer device . The temperature of the electrolyte is 70°C, and the temperature of the impure aqueous solution (Shenzhen Bay seawater) is 45°C. The seawater is calculated as 0.5M NaCl, its vapor pressure at room temperature is 10.47kPa, the vapor pressure of KOH solution is 10.07kPa when the concentration is 50wt%, and the vapor pressure difference between the two is about 0.4kPa. The test was carried out under the condition of 250mA/cm ² , and the experimental results are shown in Figure 7. As shown in Figure 7, the device has been running stably in Shenzhen Bay seawater for 100 hours, and the actual voltage of the stack is about 1.8V. It shows that the system can realize efficient hydrogen production at different solution temperatures.

Using other embodiments of the system, the method steps are the same as in Embodiment 6, and the differences are shown in Table 7:

The invention constructs an electrolytic hydrogen production system without pure water, and can directly obtain pure water from various impure waters such as seawater, river water, lake water, silt, and swamps through electrolytes for hydrogen production. This invention fundamentally solves the problems of ion exchange membrane failure, catalyst deactivation, alkaline precipitation and toxic gas due to the complex ion composition; it avoids the problem of large-scale purification system occupying a large space; at the same time, it will help the future The conversion of hydrogen energy is not limited by time and space, providing strong technical support for the direct production of hydrogen from impure aqueous solutions.

All features disclosed in all embodiments in this specification, or steps in all implicitly disclosed methods or processes, except for mutually exclusive features and/or steps, can be combined and/or extended and replaced in any way.

The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any form. According to the technical essence of the present invention, within the spirit and principles of the present invention, any simple changes made to the above embodiments The modification, equivalent replacement and improvement, etc., all still belong to the protection scope of the technical solution of the present invention.

Claims (15)

1. An electrolytic hydrogen production system without pure water, characterized in that the system includes an energy supply module, an electrolytic hydrogen production module and an electrolyte circulation regeneration module, wherein: The energy supply module is connected with the electrolytic hydrogen production module; it is used to provide electric energy for the hydrogen production reaction; Electrolytic hydrogen production module, which includes an electrolytic cell, after the electrolyte is passed into the electrolytic cell, a redox reaction occurs, water is consumed, and hydrogen and oxygen are produced; The electrolyte cycle regeneration module is connected with the electrolysis hydrogen production module; it is used to directly use impure aqueous solution to replenish pure water to the electrolyte. 2. The electrolytic hydrogen production system without pure water according to claim 1, wherein the energy source of the energy supply module is electricity converted from traditional coal electricity or renewable energy. 3. The electrolytic hydrogen production system without pure water as claimed in claim 1, characterized in that: the electrolytic cell is any one of alkaline electrolytic cell, PEM electrolytic cell, AEM electrolytic cell, or any one A combination of electrolytic cells connected in series or in parallel. 4. The electrolytic hydrogen production system without pure water as claimed in claim 1, characterized in that: the electrolyte circulation regeneration module includes a mass transfer device without energy consumption; in order to realize the "liquid-gas-liquid" phase change migration process module, use The impure aqueous solution directly adds pure water to the relatively high-concentration electrolyte solution. 5. The electrolytic hydrogen production system without pure water as claimed in claim 4, characterized in that: the energy-free mass transfer device is a device that divides the space into an electrolyte mass transfer chamber and an impure aqueous solution mass transfer chamber by a waterproof and breathable layer; When the electrolyte and the impure aqueous solution flow close to the waterproof and breathable layer, the interface vapor pressure difference between the two causes the impure aqueous solution to undergo a phase change and gasify, and the generated water vapor enters the electrolyte mass transfer chamber through the waterproof and breathable layer, and flows at the interface. Under the action of vapor pressure difference, water vapor is induced to liquefy and undergo a secondary phase change, realizing the process of "liquid-gas-liquid" phase change and migration; in addition, the waterproof and breathable layer blocks the impurities in the impure aqueous solution, and prevents the electrolyte and impure aqueous solution from interpenetrating pollution. 6. The electrolytic hydrogen production system without pure water as claimed in claim 5, wherein the impure aqueous solution filled in the impure aqueous solution mass transfer chamber is selected from seawater, river water, lake water, waste water or domestic sewage. 7. The electrolytic hydrogen production system without pure water as claimed in claim 5, characterized in that: the waterproof and breathable layer is a commercially mature waterproof and breathable layer, or any one selected from porous TPU membranes, PDMS, and PTFE membranes, Or graphene, PVDF particles, PTFE particles prepared by spraying, screen printing or electrostatic adsorption process porous waterproof breathable mass transfer layer. 8. The electrolytic hydrogen production system without pure water as claimed in claim 3, characterized in that: the electrolyte filled in the electrolyzer is a liquid electrolyte or a solid gel electrolyte; wherein the liquid electrolyte has a lower saturated water vapor pressure or has A liquid with the function of absorbing water vapor; the solid electrolyte is a substance that can induce phase change and liquefaction of water vapor. 9. The electrolytic hydrogen production system without pure water according to any one of claims 1-8, characterized in that: the system also includes a hydrogen collection module and an oxygen collection module; wherein the hydrogen collection module includes a hydrogen separator, a hydrogen scrubber The oxygen collector, hydrogen cooler and hydrogen storage tank; the oxygen collection module includes an oxygen separator, an oxygen scrubber, an oxygen cooler and an oxygen storage tank; the hydrogen separator and the oxygen separator are respectively connected to the electrolyzer, and after the hydrogen separator A hydrogen scrubber, a hydrogen cooler and a hydrogen storage tank are connected; an oxygen scrubber, an oxygen cooler and an oxygen storage tank are connected in sequence after the oxygen separator. 10. The electrolytic hydrogen production system without pure water as claimed in claim 9, characterized in that: the system also includes a cooling module, which includes a radiator, a cooling water tank and a cooling water pump; the cooling water tank is connected with the radiator, and The cooling water pump is connected with hydrogen separator, hydrogen scrubber, hydrogen cooler, oxygen separator, oxygen scrubber, oxygen cooler and heat exchanger to provide cooling water. 11. The electrolytic hydrogen production system without pure water as claimed in claim 10, characterized in that: the electrolyte pumped out of the electrolyzer, and the collected in the hydrogen separator, oxygen separator, hydrogen scrubber and oxygen scrubber The electrolyte, after passing through the heat exchanger and filter, enters the energy-free mass transfer device. 12. The electrolytic hydrogen production system without pure water as claimed in claim 10 or 11, characterized in that: an impure aqueous solution temperature controller is set between the impure aqueous solution circulation pump and the energy-free mass transfer device, and the impure aqueous solution is controlled by Temperature control of aqueous solution to adjust the vapor pressure of impure aqueous solution. 13. The electrolytic hydrogen production system without pure water as claimed in claim 12, characterized in that: each module in the system is connected with a control system for automatic control process. 14. An electrolytic hydrogen production system without pure water, characterized in that the system includes an energy supply module, an electrolyzer, a hydrogen separator, a hydrogen scrubber, a hydrogen regulating valve, a hydrogen check valve, a hydrogen cooler, and a hydrogen storage tank , oxygen separator, oxygen scrubber, oxygen regulating valve, oxygen check valve, oxygen cooler, oxygen storage tank, radiator, cooling water tank, cooling water pump, heat exchanger, filter, energy-free mass transfer device, electrolyte circulation Pump, electrolyte check valve, electrolyte temperature controller, non-pure aqueous solution check valve and impure aqueous solution circulation pump; wherein, the energy-free mass transfer device is separated into an electrolyte mass transfer chamber and a non-pure aqueous solution mass transfer chamber by a waterproof and breathable layer Chamber; the energy supply module is connected to the cathode and anode of the electrolyzer to provide electric energy; a hydrogen separator is installed on the cathode side of the electrolyzer, and a hydrogen scrubber, a hydrogen regulating valve, a hydrogen check valve, and a hydrogen cooling are installed in sequence after the hydrogen separator An oxygen separator and a hydrogen storage tank; an oxygen separator is installed on the anode side of the electrolyzer, and an oxygen scrubber, an oxygen regulating valve, an oxygen check valve, an oxygen cooler and an oxygen storage tank are arranged in sequence after the oxygen separator; the electrolyzer, the hydrogen separation Both the oxygen separator and the oxygen separator are connected to the heat exchanger, and the heat exchanger is connected to the filter and then connected to the energy-free mass transfer device; the energy-free mass transfer device is connected to the electrolyte thermostat through the electrolyte circulation pump and the electrolyte check valve, and the electrolyte The thermostat is connected to the electrolytic cell; the impure aqueous solution enters the energy-free mass transfer device through the impure aqueous solution circulation pump and check valve; the cooling water tank is connected with the hydrogen separator, hydrogen scrubber, hydrogen cooler, and oxygen separator respectively through the cooling water pump , oxygen scrubber, oxygen cooler and heat exchanger connections. 15. Utilize the electrolytic hydrogen production system without pure water as claimed in claim 14 to carry out the electrolytic hydrogen production process without pure water, which is characterized in that it comprises the following steps: First, the electrolyte is passed into the cathode, or anode, or cathode and anode of the electrolytic cell, and the electrolyte is simultaneously passed through, and a redox reaction occurs to generate hydrogen and oxygen; If the electrolytic cell is an alkaline electrolytic cell or an AEM electrolytic cell, the electrolyte first undergoes a reduction hydrogen evolution reaction at the cathode, and the generated ^OH- enters the anode through the diaphragm or anion exchange membrane, and undergoes an oxidation reaction to generate oxygen; if the electrolytic cell is a PEM electrolytic cell , then the electrolyte first undergoes an oxidation and oxygen evolution reaction at the anode, producing H ⁺ that enters the cathode through the proton exchange membrane, and undergoes a reduction reaction to generate hydrogen; The generated hydrogen and oxygen enter the hydrogen separator and the oxygen separator respectively. This process separates the generated hydrogen and oxygen from the electrolyte or moisture; the separated hydrogen and oxygen enter the hydrogen scrubber and the oxygen scrubber respectively. The process further fully cleans the unseparated electrolyte and water in the gas; the cleaned hydrogen enters the hydrogen cooler to dry and cool the hydrogen under the control and regulation of the hydrogen regulating valve and check valve, and then stores it in the hydrogen storage tank ;The cleaned oxygen enters the oxygen cooler to dry and cool the oxygen under the control and regulation of the oxygen regulating valve and the check valve, and then stores it in the hydrogen storage tank; The reacted electrolyte in the electrolyzer, as well as the electrolyte separated and recovered from the hydrogen separator, hydrogen scrubber, oxygen separator and oxygen scrubber, all pass through the heat exchanger and remove possible impurities in the filter; except The impurity electrolyte enters the electrolyte chamber in the energy-free mass transfer device, and the impure aqueous solution chamber is continuously fed into the impure aqueous solution chamber. The two chambers are separated by a waterproof and breathable layer, which only allows water vapor to pass through. Liquid water is not allowed to penetrate and pollute each other; at this time, when the electrolyte and the impure aqueous solution pass through the energy-free mass transfer device at the same time, under the action of the vapor pressure difference between the two interfaces, the impure aqueous solution is vaporized on the surface of the waterproof and breathable layer to produce water Steam and water vapor enter the electrolyte side through the waterproof and breathable layer, and under the action of the interface vapor pressure difference, induce the phase change of the water vapor to liquefy into the electrolyte to replenish water; the electrolyte replenished with water recirculates into the electrolytic cell for electrolysis.

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